Process for tinting laundry chemicals



United States Patent "ice 3,123,565 PROCESS FOR TINTING LAUNDRY CHEMICALS IN THE DRY STATE William A. Millsaps, Philadelphia, and Julian L. Stauhly,

Oreland, Pa., assignors to Pennsalt Chemicals Corporation, Philadelphia, Pin, a corporation of Pennsylvania No Drawing. Filed May 10, 1960, Ser. No. 27,987

4 Claims. (Cl. 252-135) This invention is directed to a process for tinting laundry chemicals.

For manyyears laundry sours have been tinted with a blue dye. This blue color was obtained by dispersing a pigment dye of the proper tint in water and metering the dispersed dye in the desired proportions to wet zinc silicofluoride, usually in the form of a wet cake following deliquoning of a crystal slurry. Following the addition of the aqueous dye dispersion the wet zinc silicofluoride was blended and dried, usually in a rotary kiln, to yield tinted crystals having a uniform light blue color.

The needs of commercial laundries today are so diverse that normally a single manufacturer will no longer produce all of the chemicals required by laundries but will buy them from other producers and repackage them for resale. For example, today a laundry will use soda ash, sodium tripolyphosphate, sodium hydroxide as neutralizing agents, detergents and soap builders. The fluosilicates, sodium bifluoride and ammonium chloride find use alone or in combination as laundry sours. To assist the commercial laundry user in identifying these different chemicals in the laundry room the manufacturer or supplier now tints these various chemicals.

The water insoluble dyes and pigments used for tinting laundry chemicals are conveniently supplied by the dye manufacturers as aqueous dispersions. These dispersions are quite concentrated and are usually in paste form.

When we applied these concentrated dye pastes to the dry laundry sours and alkalis and blended them, we did not obtain uniformly colored materials. We then found that this ditficulty could be overcome by adding larger quantities of water. This resulted in satisfactory tinting of the chemicals, but it made them so wet that they could not be packaged and stored without a subsequent drying operation. Since it was necessary to avoid a separate drying operation, some other means were then sought to secure satisfactory tinting of these laundry chemicals.

We have now discovered that if the dye paste is added to a liquid wetting agent and then blended with the laundry chemical, satisfactory tinting of these chemicals can be obtained. This eliminates the necessity of adding large quantities of water which wet the product and which must then be removed by a drying operation.

We have found that a least 0.25 par-ts by weight of dye paste is required to color 10,000 parts by weight of a laundry chemical such as a laundry sour or alkaline detergent provided that this amount of dye is dispersed in a wetting agent. The minimum amount of wetting agent needed to disperse this amount of dye is 0.25 part by weight per 10,000 parts by weight of the laundry chemical being tinted. Hence it will be seen that the preferred minimum ratio of dye parts and liquid wetting agent is a weight ratio of 1:1. Larger amounts of dye can be used to secure a deeper tint according to the desires of the user. Similarly, larger amounts of wetting agent may be used. However, no significant advantages are obtained with larger amount of wetting agent except added costs. Moreover, if too much of the wetting agent is added to the laundry chemical, the product will become soggy and caked andwill be unsuitable for packaging and storage.

Satisfactory dyes and pigments which we have used 3,123,555 Patented Mar. 3, 1964 to tint laundry chemicals are copper tetrabenzoporphyrazine pigment, Color Index No. 74,160 (e.g. Heliogen Blue BA0F paste), polychloro copper tetrabenzoporphyrazine dye pigment, Color Index No. 74,260 (e.g. Calcotone Green G paste), 3-hydroxy-4-(4-nitrotolyl-2- azo) Z-naphthanilide, a scarlet dye, and calcined iron oxide pigment (e.g. Calcotone Red-MB paste).

Other dyes and pigments in powder or paste form similar to those enumerated above, will suggest themselves to the worker skilled in the art.

The wetting agents which have been found to be satisfactory in dispersing these dye paste concentrates in the laundry chemicals may be a liquid of either a nonionic, cationic or anionic type. Representative nonionic wetting agents which We have found satisfactory for this purpose are the polyethylene glycol alkylphenyl ethers of which the ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) is representative. An ester type of nonionic wetting agent is so-rbitan monooleate sold under the trade name Span by Atlas Powder Company. A cocoanut fatty acid alkylol amide condensate, another nonionic wetting agent which has been satisfactorily used in conjunction with the tinting of laundry chemicals is the Alrosol C sold by the Alrose Chemical Company.

Two tertiary amine type of cationic wetting agents which we have used for this purpose are Ethomeen S/ 15 and Ethomeen 18/15. These are soybean and stearyl amine polyoxyethylene condensates (respectively) in which either the stearyl or soybean alkyl group and two polyoxyethylene groups totaling 5 ethylene oxide groups are attached to the nitrogen atoms.

The anionic wetting agents are also satisfactory for tinting laundry chemicals. Castor oil sul-fonate and Sulfonate 0.8., a mixed alkyl aryl sulfonate having the empirical formula C H SO Na are examples of this type of wetting agent that we have used.

While as little as 0.25 part of the dye and 0.25 part of the wetting agent per 10,000 parts of the laundrying chemical are satisfactory for tinting of the chemicals, it is preferred to add the materials at a slightly higher concentration. A preferred amount of dye would be 0.2 part by weight per 1000 of laundry chemical (equivalent to 2 parts by weight per 10,000 parts by weight of laundry chemical), with 3.0 parts by weight of liquid wetting agent per 1,000 parts by weight of laundry chemical (equivalent to 30 parts by weight of liquid wetting agent per 10,000 parts by weight of laundry chemical). Hence it will be seen that the preferred maximum ratio of dye parts to liquid wetting agent is .2 in 3 or 2 in 30 or a weight ratio of 1:15. A convenient way of adding the wetting agent and dye to the laundry chemical is to mix the dye paste with an equal part by weight of the wetting agent in a suitable dispersing apparatus. Thereafter, an additional quantity of wetting agent may be added to the mixture which is then added to the laundry chemical in a blending apparatus such as a sigma arm mixer, ribbon blender or conical mill blender. The mixing is continued for a sufficient time, usually about 10 minutes, for the laundry chemical to obtain a uniform hue or tint corresponding to the dye being used.

When the dye is added by itself to the laundry chemical without the addition of the wetting agent, the dye deposits as a colored speck or impurity in the chemical and will not tint to any extent whatsoever. However, when suitably mixed in a wetting agent, the small amount of dye will readily color a large quantity of laundry chemical.

It will be apparent to those skilled in the art that other components in laundry chemicals may be added or 8,1 a QB incorporated in the composition without detracting from the efiicacy of the tinting process. For examples drying agents, anti-caking agents and perfumes are often incorporated into laundry chemicals, and these will not interfere with the tinting process described above.

The letters Cl. refer to a standard color index published by Society of Dyers and Colors, 30 Pearl Assurance Building, Bradford, Yorkshire, England, 1922 24 edition. These letters identify a chemical type rather than a shade.

Cl. 74,160 identifies the copper derivative of tetrabenzoporphyrazine.

C.I. 74,260 identifies the polychloro copper derivative of tetrabenzoporphyrazine containing 15 to 16 chlorine atoms.

The best mode of practicing our invention will become apparent as set forth in the following examples in which the parts are by weight and which are given by way of illustration and not by way of limitation.

Example 1 The following mixture of laundry sours was tinted with calcined iron oxide dye paste purchased under name of Calcotone Red MB paste using the nonionic wetting agent ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units):

Parts Ammonium silicofiuoride 77.678

Ammonium chloride 22.00 Ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) 0.300

Perfume 0.002 Calcined iron oxide paste (Calcotone Red MB paste) 0.02

Example 2 A similar laundry sour mixture was tinted with Heliogen Blue BA-CF paste dye:

Parts Ammonium silicofluoride 69.695

Ammonium chloride 30.000 Ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) 0.300 Blue dye paste, (3.1. 74,160 (Heliogen Blue BA-CF paste) 0.005

Example 3 An ester type of nonionic wetting agent, sorbitan monooleate, was used by first mixing it with Heliogen Blue BA-CF paste in 30 to 1 proportion of nonionic to dye paste and thereafter adding the dispersed dye to a mixture of laundry sour chemicals as follows:

Parts Ammonium .fluosilicate 69.7 Ammonium chloride 30.0 Sorbitan monooleate (Span 80) 0.3

Blue dye paste, Cl. 74,160 (Heliogen Blue BA-CF dye paste) 0.0 1

Example 4 A mixture of ammonium fluosilicate and ammonium chloride was tinted a blue color using a dispersion of Heliogen Blue BA-OF dye paste in a fatty alkylol amide condensate as follows:

Parts Ammonium fluosilicate 69.7 Ammonium chloride 30.0 Alrosol C 0.3 Blue dye paste, C.l. 74,160 (Heliogen Blue BA- Example 5 A mixture of alkaline detergents was tinted a blue color with Heliogen Blue BA-CF dye dispersed in a noneases ionic wetting agent, ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units):

Parts Soda ash 50 Sodium tripolyphosphate 50 Ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) 0.6 Blue dye paste, Cl. 74,160 (Heliogen Blue BA Example 6 An alkaline detergent mixture was tinted a light blue by adding to it a dispersion of Heliogen Blue BA-CF dye paste dispersed in ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) as follows:

Parts Flake sodium hydroxide 50 Granular sodium orthosilicate 50 Ethylene oxide condensate of nonyl phenol (average of l0 ethylene oxide units) 0.3 Blue dye paste, Cl. 74,160 (Heliogen Blue BA- Example 7 A mixture of laundry sours was tinted a light green with Calcotone Green G paste dispersed in ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units):

Parts Ammonium fiuosilicate 69.7

Ammonium fluoride 30.0 Ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) 0.3 Green dye paste, Cl. 74,260 (Calcotone Green G paste) 0.01

Example 8 The same laundry sour combination was satisfactory colored a scarlet by using 3-hydroxy 4(4 -nitrotolyl-2- azo) Z-naphthanilide dye in the same proportions and manner as the green dye paste in Example 7.

Example 9 The importance of premixing the dye paste and wetting agent was determined in the following experiments wherein dry pigment was first blended with the sour combination after which the Wetting agent was added and the blending continued. No tinting of the sour mixture was obtained and instead the blue dye appeared as discreet particles throughout the sour.

Parts Ammonium fluosilicate 69.7

Ammonium chloride 30.0 Ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) 0.3

Example 10 A rust dissolving sour was satisfactorily tinted with Heliogen Blue BACF (blue dye paste, Cl. 74,160)

dispersed in ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units):

Parts Sodium bifiuoride 50 Sodium fl-uosilicate 50 Ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) 0.6

Blue dye paste, C11. 74,160 (Heliogen Blue BA- Example 11 A mixture of equal parts of zinc fiuos-ilicate and magnesium fluosilicate was tinted in the same manner as the sours in Example 10.

Example 12 Heliogen Blue BACF dye paste was dispersed in a cationic Wetting agent and thereafter satisfactorily used to tint a mixture of laundry sour chemicals:

Parts Ammonium silicofiuoride 69.7

Ammonium chloride 30.0 Soybean amine polyoxyethylene condensate (Ethomeen S/15) 0.3

Blue dye paste, Cal. 74,160 (Heliogen Blue BA- Example 13 In the same manner as Example 12, stearyl amine polyoxyethylene condensate, a cationic type of wetting agent having a stearyl group and two polyoxyethylene groups totaling 5 ethylene oxide groups attached to a nitrogen atom was used to disperse calcined iron oxide paste and thereafter used to satisfactorily tint the laundry sour mixture of Example 12.

Heliogen Blue BACF was satisfactory dispersed in Sulfonate OS, an anionic sulfonated petroleum oil, and used to tint a mixture of laundry sour chemicals.

Parts Ammonium fluosilicate 69.7

Ammonium chloride 30.0

Sulfonate OS, empirical formula: C H SO Na 0.3 Blue dye paste, CHI. 74,160 (Heliogen Blue BA- Example 14 In this experiment an anionic wetting agent was used in combination with a mixture of rust dissolving sours:

Parts Sodium bifluoride 50 Sodium silicofluoride 50 Sulfonated castor oil T, trade name 0.6 Green dye paste, Cal. 74,260 (Calcotone Green G paste) 0.02

Example 15 A mixture of sour chemicals was satisfactorily tinted with calcined iron oxide paste (Calcotone Red MB) paste by first blending 2 parts of Calcotone Red MB paste with 2 parts of the ethylene oxide condensate of nonyl phenol (average of ethylene oxide units). Thereafter an additional 28 parts of ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) was added to the dispersion of the wetting agent and dye paste and after intimate mixing the Whole mixture was added to a mixture of 8500 parts of ammonium silicofluoride and 1500 parts of ammonium chloride. Mixing was continued in a ribbon blender until a uniform evenly tinted pink product was obtained.

6 Example 16 Calcined iron oxide (Calcotone Red MB) paste was added to a mixture of 8500 parts of ammonium silico fluoride and 1500 parts of ammonium chloride without any wetting agent. The Calcotone Red MB paste was added at 2 parts by Weight. After blending for 30 minutes, no color was obtained whatsoever. Thirty parts of ethylene oxide condensate of nonyl phenol (average of 10 ethylene oxide units) was then added and mixing was continued for an additional 15 minutes. No satisfactory color was obtained from this procedure.

We claim:

1. The process of tinting a laundry chemical in the dry state, said laundry chemical selected from the group consisting of ammonium fluosilicate, zinc tluosilicate, magnesium fluosilicate, sodium iluosilicate, ammonium chloride, sodium bifluoride, sodium tripolyphosphate, sodium carbonate, sodium orthosilicate and sodium hydroxide, comprising first mixing a water insoluble dye in paste form with a liquid wetting agent selected from the group consisting of anionic, nonioni-c and cationic wetting agents, the ratio of dye paste to liquid wetting agent being within the range of from about 1:1 to about 1:15 by weight, and thereafter blending at least 0.005 parts by weight of the mixture of dye paste and liquid wetting agent with parts by weight of said laundry chemical until the tint of said dye develops on the laundry chemical.

2. The process of claim 1 in which the water insoluble dye in paste form is selected from the group consisting of blue dye paste, C.I. 74,160, green d-ye paste, C.I. 74,260, calcined iron oxide paste, and 3-hydroxy-4-(4- nitrolyl-2-azo)-2-naphthanilide paste.

3. The process of tinting a laundry sour composition comprising dispersing water insoluble calcined iron oxide in paste form in 30 parts by Weight of the ethylene oxide condensate of nonyl phenol having an average of 10 ethylene oxide units, and blending this dispersed dye with a mixture of 7,700 parts by weight of ammonium silicofiuoride and 220 parts by weight of ammonium chloride until a uniform pink tint is obtained.

4. The process of tinting a laundry sour composition comprising dispersing water insoluble blue dye, C.I. 74,160, in paste form in 30 parts by weight of the ethylene oxide condensate of nonyl phenol having an average of 10 ethylene oxide units, and blending this dispersed dye with a mixture of 6970 parts by weight of ammonium fluosilicate and 3000 parts by weight of ammonium chloride until a uniform light blue tint is obtained.

References Cited in the file of this patent UNITED STATES PATENTS 1,849,535 Phair Mar. 15, 1932 1,970,578 Schoelle-r et a1 Aug. 21, 1934 2,141,589 Bishop Dec. 27, 1938 2,893,818 Millsaps et a1. July 7, 1959 OTHER REFERENCES Condensed Chemical Dictionary, Reinhold Pub. C0,, N.Y., 5th ed., 1956, page 1128.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N00 3, 123,,565 March 3 1964 William A, Millsaps et a1,

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6, line 41,, for "220" read 2200 Signed and sealed this 30th day of June 1964c (SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. THE PROCESS OF TINTING A LAUNDRY CHEMICAL IN THE DRY STATE, SAID LAUNDRY CHEMICAL SELECTED FROM THE GROUP CONSISTING OF AMMONIUM FLUOSILICATE, ZINC FLUOSILICATE, MAGNESIUM FLUOSILICATE, SODIUM FLUOSILICATE, AMMONIUM CHLORIDE, SODIUM BIFLUORIDE, SODIUM TRIPOLYPHOSPHATE, SODIUM CARBONATE, SODIUM ORTHOSILICATE AND SODIUM HYDROXIDE, COMPRISING FIRST MIXING A WATER INSOLUBLE DYE IN PASTE FORM WITH A LIQUID WETTING AGENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC, NONIONIC AND CATIONIC WETTING AGENTS, THE RATIO OF DYE PASTE TO LIQUID WETTING AGENT BEING WITHIN THE RANGE OF FROM ABOUT 1:1 TO ABOUT 1:15 BY WEIGHT, AND THEREAFTER BLENDING AT LEAST 0.005 PARTS BY WEIGHT OF THE MIXTURE OF DYE PASTE AND LIQUID WETTING AGENT WITH 100 PARTS BY WEIGHT OF SAID LAUNDRY CHEMICAL UNTIL THE TINT OF SAID DYE DEVELOPS ON THE LAUNDRY CHEMICAL. 